Perfluoroalkyl groups containing polymerisation products

ABSTRACT

wherein Rf represents an unbranched or branched perfluoroalkyl radical with 3 to 12 carbon atoms, R represents hydrogen or fluorine, and R1 and R2 represent hydrogen or methyl and m is 1 or 2, n is a whole number from 2 to 12, and p is a whole number from 1 to 3, and optionally of other copolymerisable, ethylenically unsaturated monomeric compounds are provided. The polymerisation products can be homopolymers or copolymers. The polymerisation products are useful for producing oleophobic, hydrophobic or dirt repellent finishes on various substrates.   Polymerisation products of at least one perfluoroalkylalkyl ester of the formula

United States Patent [1 1 Jager et a1.

1 1 PERFLUOROALKYL GROUPS CONTAINING POLYMERISATION PRODUCTS [75]inventors: Horst .liiger, Bettingen; Paul Schiifer, Richen, both ofSwitzerland [73] Assignee: Ciba-Geigy AG, Basel Switzerland [22] Filed:Sept. 17, 1973 [21] Appl. No: 397,522

[30] Foreign Application Priority Data Sept. l2 1973 Switzerland13054/73 117/155; 117/161; 260/285 D; 260/47 UA;

260/63 UY; 260/785 R; 260/785 B;

260/835; 260/855 ES; 260/861 N; 260/861 [51] Int. C137. C08F 3/64; C08F3/66; C08F 15/16 [58] Field of Search 260/895 A 8943, 861 R, 260/861 N,8601 E 86.3, 86.7

[56] References Cited UNITED STATES PATENTS 3.248.260 4/1966 Langerak cla1 l V r r l v, 1 17/161 1 Nov. 11, 1975 3.457247 7/1969 Katsushima cta1 H 260/895 H Primary E.\'aminerHarry Wong, Jr.

Attorney, Agent, or Firm-Joseph G. Kolodny; Prabodh 1. Almaula; EdwardMcC. Roberts [57] ABSTRACT Polymerisation products of at least oneperfluoroalkylalkyl ester of the formula The polymerisation products areuseful for producing oleophobic, hydrophobic or dirt repellent finisheson various substrates.

15 Claims, No Drawings PERFLUOROALKYL GROUPS CONTAINING POLYMERISATIONPRODUCTS Monomers containing perfluoroalkyl groups, their correspondingpolymerisation products and their use as agents for rendering materialsoleophobic and hydrophobic are already known. Homopolymers andcopolymers that are derived from pertluoroalkylacrylic or methacrylicesters of the formula wherein R represents hydrogen or methyl and .x isa number from about 3 to 20 are already known from various patents, e.g.US. Pat. Nos. 3,248,260 and 3,282,905, British Pat. No. 1,095,900,German Pat. No. l,469,45l, or Swiss Pat. No. 504,577.

From US. Pat. No. 3,002,765 there are also known polymers thatarenbtained by polymerisation of acrylates and methylacrylates of theformula wherein R represents hydrogen or methyl, R represents loweralkyl and x is a whole number from about 3 to 20.

The known homopolymers and copolymers produce useful oleophobic andhydrophobic effects, but the application amounts of the respectivepolymers are relatively large. The present invention is based on theobservation that it is possible to interrupt the perfluoroalkyl chainsin the starting monomers by fluorine-free members, e.g. Cl-l, groups,without any impairment of the effect occurring with the application ofthe corresponding polymers, although the amount of fluorine responsiblefor the repellent effect is diminished. Further, the new polymerisationproducts are characterised by a very good repellent property in thatthey produce very good effects when used in very small amounts (asfluorine deposit on the fibre).

The present invention provides polymerisation products of at least oneperfluoroalkylalkyl ester of the formula wherein R; represents anunbranched or branched perfluoroalkyl radical with 3 to 12 carbon atoms,R represents hydrogen or fluorine and R, and R, represent hydrogen ormethyl and m is l or 2, n is a whole number from 2 to 12, and p is awhole number from 1 to 3, and optionally of other copolymerisable,ethylenically unsaturated monomeric compounds. The polymerisationproducts can be homopolymers or copolymers.

The perfluoroalkyl radical in formula (1) can be an unbranched or abranched radical with 3 to [2, preferably 4 to 10, carbon atoms, andcorrespond approximately to the following formulae:

wherein R,, R, R R m, n, and p have the indicated meanings.

Particular interest attaches to such homopolymers that contain recurringunits of the formulae wherein R represents hydrogen or fluorine, and R,and R, represents hydrogen or methyl, n is a whole number from 4 to 10and p is a whole number from I to 3.

In addition to the cited units for the homopolymers, the copolymerscontain recurring units of other ethylenically unsaturatedcopolymerisable compounds. The number of recurring units can be about 10to 400. The

-molecular weight range is accordingly about 5000 to 230,000.

The manufacture of the starting monomers of the formula l) is carriedout by known methods. These compounds are therefore obtained e. g. byreaction of the corresponding perfluoroalkylalkyl iodides withunsaturated monobasic acids or derivatives thereof in the presence ofoleum or by reaction of the corresponding perfluoroalkylalkyl nitrateswith the unsaturated acids in the presence of sulphuric acid. Suitableacids are e.g. acrylic, methacrylic, crotonic, and vinylacetic acids.

The polymerisation of the monomeric pertluoroalkylalkyl esters can takeplace in solution or in emulsion and in the presence of catalysts thatliberate free radicals with themselves, with anotherperfluoroalkylallryl ester or with other compounds that can bepolymerised to linear polymers.

Examples of suitable compounds for the copolymerisation with thepertluoroalkylalkyl esters are:

a. vinyl esters of organic carboxylic acids, e.g. vinyl acetate, vinylformate, vinyl butyrate, vinyl benzoate,

b. vinyl alkyl ketones and vinyl alkyl ethers, such as vinyl methylketone and vinyl butyl ether,

c. vinyl halides, such as vinyl chloride, vinyl fluoride, vinylidenechloride,

d. vinylpyrrolidone,

e. vinyl aryl compounds, e.g. styrene and substituted styrenes,

f. derivatives of the acrylic acid series, e.g. acrylic nitrile oracrylic amide and preferably derivatives substituted at the amidenitrogen, e.g. N-methylolacrylamide, N-methylolacrylic amide alkylether, N,N-dihydroxyethylacrylic amide, N-tert.butyl-acrylic amide andhexametholylmelamine triacrylic amide, and the corresponding quaternisedcompounds,

g. esters of the acrylic acid series, e.g. esters of acrylic acid,methacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid,fumaric acid or itaconic acid, and monoor dialcohols containing from 1to l8, preferably 8 to 12 carbon atoms, or phenols, e.g. ethyl acrylate,glycidyl acrylate, butylacrylate, acrylic acid monoglycol ester ordodecylacrylate, or N-dialkylaminoethylmethacrylate and thecorresponding quatemised compound, and

h. polymerisable olefines, such as isobutylene, butadiene or2-chlorobutadiene,

i. monomers containing periluoroalkyl groups, such as compounds of theformulae C F CH CH,OOC CH,

and

wherein a is a whole number from 4 to 18, R, represents hydrogen ormethyl, R represents hydrogen, methyl, or ethyl.

Preferably there are used esters, amides or methylol amides of acrylicor methacrylic acid, such as ethyl acrylate, hydroxyethyl acrylate andhydroxymethyl acrylate, butyl acrylate, glycidyl acrylate,glycolmonoacrylate, acrylic amide, methacrylate, methacrylic amide,N-methylolacrylic amide, N-methylolacrylic methyl ether,N-tert.butylacrylic amide; vinyl esters of organic carboxylic acids,such as vinyl acetate; styrene, vinyl halides, such as vinyl chloride orvinylidene chloride; or polymerisable olefines, such as isobutylene.

The polymers are composed as a rule of 5 to 100, preferably of 40 to 98,percent by weight of a perfluoroalkylalkyl ester and of 95 to 0,preferably 60 to 2, percent by weight of another compound. Particularindustrial importance attaches to those bi-, terand quaterpolymers thatin addition to 40 to 98 percent by weight of the monomeric carboxylicacid perfluoroalkyl ester, based on the weight of the monomer, contain areactive monomer, such as N-methylolacrylic amide, an acrylic ester,such as decylacrylate, and optionally a vinyl ester, such as vinylacetate.

The manufacture of the polymers by homopolymerisation orcopolymerisation of perfluoroalkylalkyl esters with one or more othercopolymerisable ethylenically unsaturated monomers is carried out byconventional methods, for example by block polymerisation, beadpolymerisation, polymerisation in aqueous emulsion or preferably bysolvent polymerisation in a solvent suitable for this purpose, e.g.acetone, benzene, sym. di-

4 chloroethane, ethyl acetate, or trifluoromethylbenzene.

The polymerisation is effected advantageously with the application ofheat, preferably to the boiling temperature of the solvent andaccompanied by the addition of catalysts that form peroxidic or otherfree radicals and are soluble in the reaction medium, e.g. benzoylperoxide, lauroyl peroxide, 01,01- azobisisobutyronitrile or potassiumperoxide disulphate or redox systems, e.g. potassium peroxidedisulphatelsodium bisulphite or ferrosulphate.

Depending on the nature of the polymerisation conditions and of themonomeric starting materials used, the polymeric compounds are obtainedin the form of emulsions.

It is furthermore also possible to carry out the polymerisation of themonomeric compounds in the presence of substrates. For example, it canbe carried out on glass fibre fabrics or textile material. In this casethe respective substrate is advantageously impregnated with solutions oremulsions of the monomers and subsequently the polymerisation iseffected by addition of a polymerisation catalyst by heating thematerial.

The preferred polymerisation processes are emulsion polymerisation in anaqueous medium and solvent polymerisation.

The polymerisation is preferably carried out with a reaction time thatis so adjusted that a virtually quantitative conversion of the monomerinto the polymer is attached. The maximum reaction time depends on thecatalyst used and the polymerisation temperature and also on otherconditions, but it is generally in the range from 0.5 to 24 hours.

The polymerisation temperature depends in turn on the chosen catalyst.In the case of emulsion polymerisation in aqueous medium it is ingeneral in the range from 20 to 90C. Whereever possible, thepolymerisation is carried out at atmospheric pressure.

In the emulsion polymerisation, the monomer(s) to be polymerised is(are) polymerised jointly in an aqueous solution of an emulsifier undernitrogen to a given monomer concentration of about 5 to about 50%.Normally the temperature is raised to 40 to C in order to effect thepolymerisation in the presence of an added catalyst. The concentrationof the polymerisation catalyst is generally between 0.1 and 2%, based onthe weight of the monomers.

Suitable emulsifiers are cationic, anionic, or nonionic surfactants. Thehydrophobic constituent of the emulsifier can be a hydrocarbon orfluorinated hydrocarbon.

Suitable cationic emulsifiers are for example quaternary ammonium salts,for example quaternary ammonium salts or amine salts that contain atleast one longchain alkyl or fluoroalkyl group, or a benzene ornaphthalene group that is highly substituted with alkyl to yield thehydrophobic constituent.

Further suitable emulsifiers are the non-ionic surfactants in which thehydrophilic constituent is a poly(ethoxy) group and the hydrophobicconstituent is either a hydrocarbon or a fluo rinated hydrocarbon group,e.g. the ethylene oxide condensates of alkylphenols, alkanols,alkylamines, alkylthiols, alkylcarboxylic acids, fluoroalkylcarboxylicacids, fiuoroalkylamides and the like. Anionic emulsifiers are forexample the sulphuric acid or phosphoric acid esters of the citedethylene oxide condensates of long-chain alkylphenols, fatty a]- cohols,and fatty amines.

In the solvent polymerisation, the monomer(s) is (are) dissolved in asuitable solvent, such as fluorinated solvents, for examplehexafluoroxylene, benzotrifluoride, or mixtures thereof with acetoneand/or ethyl acetate, and polymerised in a reaction vessel accompaniedby the use of initiators such as azobisisobutyronitrile or other azoinitiators, in concentrations of 0.1 to 2%, at 40 to 100C undernitrogen.

Preferred solvents are hexafluoroxylene, benztrifluoride, fluorinesubstituted halogenated hydrocarbons, other fluorinated solvents ans thelike.

As stated at the outset, valuable copolymers with other ethylenicallyunsaturated monomers are obtained in the polymerisation of the newmonomers in addition to homopolymers. On completion of thepolymerisation, the polymerisation products are obtained in the form ofsolutions or dispersions that have a solids content of about to wpteferably to 25,.percent by weight. It is advantageous to use thesesolutions or dis persiohs diieet, optionally in dilute form, for thevarious applications.

The homopolymers or copolymers according to the invention can be usedfor treating porous or nonpon ous substrates, pfi'rfibly' rodudin goleophobin, hydrophobic, or diet repellent sashes memes. As 10* roussubstrates there may be mentioned leadier and wood or especiallyiibreentertainments textiles and paper. Possible nonorous substrates arechiefly metal, plastic, and glass surfaces. a

The compounds sceaiai" g to the invention can a be used for ex ple asaia iilesfdi as are lubricants for the prevention of est assesses-ten,of as tives for polish r Examples aria-stale mite-ails use an ae'eererasiy treated with the monomeric or polymeric perfluoro compoundsare those from natural or regenerated cel= lulose, such as cotton,linen, or rayon, staple fibre, or cellulose acetate. Also suitable aretextiles made from wool, synthetic polyami'des, polyester, orpolyaerylonitrile. Blended fabrics or blended knitted fabrics fromcotton/polyester fibres can also be finished witli advantage. Thetextiles can be in the form of threads, fibres, flocks, fleeces, butpreferably of woven or knitted fabrics, and can be used for example asarticles of clothing, upholstery materials, deco rating materials, andcarpets.

Preparations that contain the polymeric perfluoro compounds can beapplied to the substrate in known manner. The substrates can be finishedby being treated both with solutions, such as dispersions or emulsions,of the polymeric perfluoro compounds.

Fabrics can be impregnated e.g. by the exhaustion process or on a padderthat is coated with the preparation at room temperature. The impregnatedmaterial is then dried at 60 to 120C and subsequently optionallysunjected to a heat treatment at over 100C, e.g. from 120 to 200C,advantageously in the presence of known catalysts that donate acid.

Examples of further application methods are spraying, brushing,roll-coating, dusting with subsequent heat fixing or transfer of thepolymers from an auxiliary material (paper, foil) accompanied by theapplication of heat. The compounds according to the invention areapplied in amounts of 0.1 to 10, preferably 0.5 to 5, percent by weightbased on the substrate.

It is also possible to apply still further agents to the substratessimultaneously with the compounds according to the invention, e.g.wetting a ents, soft-handle agents, water repellents, paraffin waxemulsions, resin finishes, or agents that impart crease resistance.

Besides the cited effects that can be attained with the polymersaccording to the invention it is also possible in particular to achievesoil-release and antisoiling effects on textile fibre substrates. Amongthe polymerisation products according to the invention the copolymersare particularly suitable for this purpose.

The following Examples describe the invention in more detail but are inno way limitative thereof. The parts and percentages are by weightunless otherwise stated.

EXAMPLE I a. A mixture of 30 parts of water, 0.6 part ofdodecyltrimethylammonium chloride, 0.6 part ofoctadecyltrimethylammonium chloride, 0.4 part of vinyl acetate, 0.4 partof N-niethylolacrylic amide, 5 parts of acetone and 9.2 parts of thecompound of the formula d FalA Ha zL 2 2 is heated with in a nitrogenatmosphere to C. A solution of 0.025 part of potassium peroxidedisulphate in 2.5. parts iii water is added whereupon polymerisationoccurs. Twenty minutes later a solution of 0.025 part of petassiumperoxide disulphate in 2.5 parts of Water is aga' added. The resultingemulsion is kept for 3 Boats at 70C to bring the polymerisation tocompletion. About 51 parts of a finely dispersed emulsion wifli a resincontent of 20.3% (corresponding to a yield of sea). is obtained.

* The copolymers of the following fluorinated monomer compounds aremanufactured according to procedure (a):

Remainder on impurities. Example 1(a) is a comparison example.

EXAIviPLE 2 a. A mixture of 25 parts of water, 0.6 part ofdodecyltrimethylammonium chloride, 0.6 part ofoctadecyltrimethylammonium chloride, 4.6 parts of hexylmethacrylate, 04part of N-methylolacrylic amide, 5 parts of acetone, and 5 parts of thecompound of the formula C,,F,,, ,(CH,CF,),. CH,CH O0CCH=CH, is heatedwith stirring in a nitrogen atmosphere to 60C. A solution of 0.025 partof potassium peroxide disulphate in 2.5 parts of water and a solution of0.007 part of sodium metabisulphite in 2.5 parts of water are addedwhereupon polymerisation occurs. Twenty minutes later a solution of0.025 part of potassium peroxide disulphatd in 2.5 parts of water and asolution of 0.007 part of sbdium metabisulphite in 2.5 parts of waterare added once more. The resulting emulsion is kept for 3 hdurs at 60Cto bring the polymerisation to completion. About 51 parts of a finelydisperse emulsion with a resin content of 20.3% (corresponding to ayield of 98%) is obtained.

The copolymers of the following fluorinated monomer compounds aremanufactured according to the procedure 2(a):

-continued b) C,,1-,,,..(CH,(:F,),,CH,C! 1,00CC1-1=(:1-1, 14.63C8F|,CH2CF,CH ,CH,OOCCH=CH2 C,.F,,,..,CH,C1-1,00CCH=CH, 26.00 C..1=,CH,CF,C|-1,CH,ooCCH=C1-1, c) C,.F,,..(cH,CF,),,CH,CH,00CCH=CH, 23.73C,.,F,,CH,CF,CH,CH,OOCCH#IHI d) Composition of the fluorinated monomeras l e) 5.90 C.F, -,(CH,CF,),CH,CH,OOCCH=CH2 (compartson example). 54.50 C F, (Cl-l=CF,),CH Cl-l,OOCCI-l=Cl-l e) Composition of thefluorlnated monomer 1.90 C F,.(CH,CF,),CH,CH,OOCCH=CH C..F,...r r r 0C(CH=)Cl-l, ""1 43.90 C.F,,CH,CF,cH,c1-1,o0cC1-1=CH, a 6 26.00c.,F,,cH,cF,cH,C1-I,00CCH=CH, (comparison example). 3.00CWF,ICH,CFRCHICH,OOCCH=CH, 1') Composition of the fluonnated monomer10.10 C,FH(CH,CF,),CHZCH,OOCCH=CH,

C.:F"SO,N(R' )CH,CH,00CC(CH,)=CH, 5.70 C,,F.1(CH,CF ,),CH,CH,O0CCH=CH, Rlower alkyl 1.30 c..,1=,,(c11,c1= ),cH,cH,o0cc11=c11, (comparisonexample) 5.50 C,F,,(CH,CF,),CH,CH,OOCCH=CH2 Remainder on 100%impurities.

The polymers from (6) and (f) are commercial products A llcation of theP01 mers The monomer mixture contains (analysis by gas P ychromatography 1. Cotton fabric, polyester/cotton fabric (65/35), and

various synthetic fabrics are impregnated with the following liquors14.14 C.F ,Cl-l CBC}! CH OOCCH==CH 45,94 9 C F: CH:CF CH:CH:OOCCHnCI-[:The amount of flUOl'lllB apphed 1:: between 0.075 and 3.43C..F,,CH,CF.CH,CH,OOCCl-Ia-CH 0.2 rcent b wei t the wei t the s b- 1153k C.F,,(CH,CF ),CI-l,CH.OGCCH=-C l-l, 96 Th f g based 3b of dried 7CFACHCFJICHICBOOCCH-CHI strate. e a [1C 18 impregnate on a padder, at Z:ro rJ m m E fiOCC -CW 90C and heat fixed for 30 seconds at 150C. 13 f-f, ggg g ga g The finished fabrics are tested for their 611 repellency94.8 '11. c,1=,cn,CF,cH,c1-1,0occ1-1=c1-1, by the AATCC Test Procedure 118-1966 of the Ameri- 1 5 g FP" can Association of Textile Chemists andColorists meander on 100% rm unties. it!) 26Z6%CIFI,CH,CF:CE|CH,OOCCH-CH! 111$ repellenctes are between 0 and 8,8

fg-gg 2 grf rC l g fl if t t ooc tfl-c ig being the best repellencyvalue. 30:00 CLljgumwnacpmflzcfiioocflacfl Thewater repellent propertlesare determlned quafangs-12d 0n 100%1m 11:21". ternatively on the beersof the water absorption after "'1 c F ,C11,C1-1F 1-1 H OOCCH-CH 3H9dFLCHCHFCHCHbOCCM: 30 the fabrics have been bnefly spr1nkled. Themoisture 16.27 as c,.,|=,,c1-|,c1-|1=cu,c cc -q absorption in percent byweight, based on the sohds Rcmflihd impurities ntent of the l s de Thes' l r the m, ZBMECFI'CHCH cm", 00 sagc pe 1s temunedn malei q, C'FI 1Cb peroenteges the tter the water repeent propert es.9.94%c...1=,.c11,cr1,o0cc1-1-c11. The llqLlOl' compositions and therepeliency values obtained are listed in the following table.

Table l Polymer according to la 1b 1c 1d 1e procedure Polymer in 3/1 142s 28 32 16 32 32 32 32 32 32 32 17.5 35 Aminoplast preeondens0 50 so s050 50 50 50 50 sate in 5/1 1) MgCl,.6l-l,0 g/l 8 8 8 8 8 8 8 8 8 8Extender 3/1 2) 30 30 30 Amount of flurone in percent by weight (on 0.10.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.2 the fibre material)Cotton oil repellency 6 6 5 5 4 5 6 6 5 6 2 5 3 5 Water repellency 47 476 44 3 50 107 16 Amount of fluorine in percent by weight (on 0.075 0.150.l5 0.l5 00.75 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.075 0.15 the fibrematerial) Cnttonipolyener oil repellency 5 5 5 2 2 3 5 6 5 5 5 5 l 4 7water repellency 3 6 2 l l 22 21 1 I) 50 aqueous preparation of 1 moleof hexamethylolrnelamine-hexamethyl ether and 1 male of dimethylolethylurea. 21 Paratfin wax emuilion Table 2 Polymer according in 2a 2b 2c 2d2e 2? procedure Polymer in 371 32 16 .12 62 31 62 62 31 64 32 64 32 6432 64 mim mt 50 50 s0 50 $0 50 s0 50 so 50 50 50 preeondensate in 1)9,000 a B a 8 B a s s s s a s Extender 30 30 30 30 30 Amounto fluorine0.2 0 1 0.2 0.2 0.1 0.2 0.2 0.1 0.2 0.2 0.1 0.2 0 l 0.2 0.1 0.2 inpercent by weight (on the fibre material) Cotton repeuutcy 6 s 6 6 s 6 65 6 5 4 6 0 2 1 2 water repellency 14 23 1 39 29 24 41 32 36 33 16 9%Amount offluorine 0.15 0.075 0.15 0.15 0.075 0.15 0.15 0.075 0.15 0.150.075 0.15 0.075 0.15 0.0 5 0.15

Table 2-continued Polymer according to 2a 2b 2c 2d 2e 2f procedure inpercent by weight (on the fibre material) Cotton/polyester oilrepellency 5 4 5 4 4 5 2 3 6 2 2 5 2 3 2 2 water repellency 3 2 l 8 26l9 i6 26 5 l l 18 I3 Table 3 Polymer according to 2 a 2 e 2 f procedurePolymer in gll i6 32 32 64 r 32 64 Aminoplast preconden- 50 5O 50 S 5050 sate in g/l l) M c1,.6l-|,o gl] 8 s s s s 8 Amount of fluorine inpercent by weight (on 0.075 0.15 (L075 015 0.075 0. l the fibrematerial) Oil repellency:

polyester 5 7 2 S 2 5 polyamide 5 7 2 5 2 5 polyacrylonitrile 5 7 2 6 24 We claim: 1. Homopolymers which contain about to 400 re- H l i curringunits of the formula CHCHF Cmc"! T R1 i H R,(c11, F) (3,11,,0 -(CH,),, nwherein R has the meaning given in claim 2.

5. Copolymers which contain about 10 to 400 recurring units of theformula wherein R; represents an unbranched or branched per- 35fluoroalkyl radical with 3 to 12 carbon atoms, I H

R represents hydrogen or fluorine, H R and R represents hydrogen ormethyl and I i m is l or 2, v n a number g 2 m and 40 wherein R,represents an unbranched or branched perp a w o g number 1 m rfluoroalkyl radical with 3 to 12 carbon atoms, 2. ftlgmopolymers accordng to claim l, which con- R represents hydrogen or fluorine tain a ut 10to 400 recumng units of the formula R1 and R2 represents hydrogen ormethyl and m is l or 2,

n is a whole number from 2 to 12 and i 3 p is a whole number from 1 to3, and up to 95% by CIFH P H weight of recurring units of at least oneother ethylenically unsaturated monomer compound.

6. Copolymers according to claim 5, which contain about 10 to 400recurring units of the formula wherein R represents hydrogen or fluorineand R and R represent hydrogen or methyl, n is a whole number from 4 to10, and p is a whole number from 1 to 3. i H i 3. Homopolymers accordingto claim 2, which con- -I =-a+ H tain about 10 to 400 recurring units ofthe formula 1L,

wherein R represents hydrogen or fluorine and R, and H I R, representhydrogen or methyl, n, is a whole number from 4 to 10, and p is a wholenumber from I to 3.

1 7. Copolymers according to claim 6, which contain about 10 to 400recurring units of theformula wherein R n and p have the meanings givenin claim 3.

4. Homopolymers according to claim 2, which contain about 10 to 400recurring units of the formula 1 1 wherein R,, n and p have the meaningsgiven in claim 6.

8. Copolymers according to claim 6, which contain about to 400 recurringunits of the formula wherein R, has the meaning given in claim 6.

9. Copolymers according to claim 5, wherein as comonomers there are usedmembers selected from the group consisting of esters, amides, methylolamides of acrylic or methacrylic acid, which optionally containperfluoroalkyl groups, styrene, vinyl halides, vinylidene halides, vinylesters of organic acids, and polymerisable olefines.

10. A process for the manufacture of polymerisation products accordingto claim 5, wherein perfluoroalkyl esters of the formula 8n wherein Rrepresents hydrogen or fluorine and R, and R represent hydrogen ormethyl, :1, is a whole number from 4 to 10 and p is a whole number from1 to 3, are polymerised.

12. A process according to claim 10, wherein perfluoroalkylalkyl estersof the fonnula wherein R represents hydrogen or fluorine and R and Rrepresent hydrogen or methyl, :1, is a whole number from 4 to 10, and pis a whole number from 1 to 3, are polymerised together with membersselected from the group consisting of esters, amides, methylol amides ofacrylic or methacrylic acid, which optionally contain perfluoroalkylgroups, styrene, vinyl halides and vinylidene halides, vinyl esters oforganic acids, and polymerisable olefines.

13. A process according to claim 10, wherein the polymerisation iscarried out in an organic or in an aqueous emulsion.

14. A process according to claim 10, wherein the polymerisation iscarried out in the presence of a catalyst that forms radicals.

l5. Polymerization products according to claim 5 wherein the productcontained 40 to 98% perfluoroalkylalkyl ester and 60 to 2% of the othercopolymerizable ethylenically unsaturated monomeric compound.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENTNO. 3,919,1 3

DATED November 11, 1975 |NVENTOR(S) 1 HORST JBGER ET AL It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 9, claim 3, line 6%, delete "3" and substitute Column 11, claim10, line 22, delete "8n".

En'gncd and Scaled this AMEN.

RUTH C. MASON C. MARSHALL DANN Arresting Officer (nmmissinner of Parentsand Trademarks

1. HOMOPOLYMERS WHICH CONTAIN ABOUT 10 TO 400 RECURRING UNITS OF THEFORMULA
 2. Homopolymers according to claim 1, which contain about 10 to400 recurring units of the formula
 3. Homopolymers according to claim 2,which contain about 10 to 400 recurring units of the formula 4.Homopolymers according to claim 2, which contain about 10 to 400recurring units of the formula
 5. Copolymers which contain about 10 to400 recurring units of the formula
 6. Copolymers according to claim 5,which contain about 10 to 400 recurring units of the formula 7.Copolymers according to claim 6, which contain about 10 to 400 recurringunits of the formula
 8. Copolymers according to claim 6, which containabout 10 to 400 recurring units of the formula
 9. Copolymers accordingto claim 5, wherein as comonomers there are used members selected fromthe group consisting of esters, amides, methylol amides of acrylic ormethacrylic acid, which optionally contain perfluoroalkyl groups,styrene, vinyl halides, vinylidene halides, vinyl esters of organicacids, and polymerisable olefines.
 10. A process for the manufacture ofpolymerisation products according to claim 5, wherein perfluoroalkylesters of the formula 8n
 11. A process according to claim 10, whereinperfluoroalkylalkyl esters of the formula
 12. A process according toclaim 10, wherein perfluoroalkylalkyl esters of the formula
 13. Aprocess according to claim 10, wherein the polymerisation is carried outin an organic or in an aqueous emulsion.
 14. A process according toclaim 10, wherein the polymerisation is carried out in the presence of acatalyst that forms radicals.
 15. Polymerization products according toclaim 5 wherein the product contained 40 to 98% perfluoroalkylalkylester and 60 to 2% of the other copolymerizable ethylenicallyunsaturated monomeric compound.